4,5-bis-(trifluoromethylimino)-diazoles

ABSTRACT

AND R, R&#39;&#39;, R&#34; AND R&#39;&#39;&#34; EACH IS HYDROGEN OR VARIOUS OPTIONALL FIG-03 AND R, R&#39;&#39;, R&#34; AND R&#39;&#39;&#34; EACH IS HYDROGEN OR VARIOUS OPTIONALLY SUBSTITUTED HYDROCARBON OR HETEROCYCLIC RADICALS, SEVERAL OF THEM TOGETHER POSSIBLY FORMING A HETEROCYCLIC RING. THE INVENTION ALSO EXTENDS TO COMPOSITIONS CONTAINING, AND METHODS OF USING, THE NEW COMPOUNDS TO COMBAT FUNGI, INSECTS AND ACARIDS.   =C(-R&#39;&#39;)-R&#34;   IN WHICH Z IS OXYGEN, R-N= OR   Z=C&lt;(-X-C(=N-CF3)-C(=N-CF3)-N(-R&#34;&#39;&#39;)-)   Z=C(-X-H)-NH(-R&#34;&#39;&#39;) + F3C-N=CF-CF=N-CF3 ---&gt;   4.5-BIS-(TRIFLUOROMETHYLIMINO)OXAZOLES OR DIAZOLES ARE PREPARED BY REACTING THE ENOL FORM OF AN AMIDE OR AN IMIDE OF A CARBOXYLIC ACID OR CARBONIC ACID, HAVING AT LEAST ONE HYDROGEN ATOM ON EACH OF AN OXYGEN AND NITROGEN OR TWO NITROGEN ATOMS VICINAL TO THE AMIDE CARBON ATOM, WITH PERFLUORO-2,4-DIAZAHEXA-2,4-DIENE IN THE PRESENCE OF A HYDROGEN FLUORIDE ACCEPTOR AT A TEMPERATURE OF ABOUT -50 TO 120*C., IN ACCORDANCE WITH THE FOLLOWING FORMULA

United States Patent 3,787,435 4,5-BIS-(TRIFLUOROMETHYLlMINO)-DIAZOLESHans-Joachim Scholl, Cologne, Erich Klauke, Odenthal,

Ferdinand Grewe, Burscheid, and Ingeborg Hammann, Cologne, Germany,assignors to Bayer Aktiengesellschaft, Leverkusen, Germany No Drawing.Filed Dec. 8, 1971, Ser. No. 206,159 Claims priority, applicationGermany, Dec. 18, 1970,

P 20 62 346.5 Int. Cl. C07d 49/34, 57/02 US. Cl. 260-3092 ABSTRACT OFTHE DISCLOSURE 4,5-bis-(trifluoromethylimino)oxazoles or diazoles areprepared by reacting the enol form of an amide or an imide of acarboxylic acid or carbonic acid, having at least one hydrogen atom oneach of an oxygen and nitrogen or two nitrogen atoms vicinal to theamide carbon atom, with perfluoro-2,5-diazahexa-2,4-diene in thepresence of a hydrogen fluoride acceptor at a temperature of about 50 to120 C., in accordancewith the following formula and R, R, R" and R'"each is hydrogenor various optionally substituted hydrocarbon orheterocyclic nadicals, several of them together possibly forming aheterocyclic ring.

The invention also extends to compositions containing, and methods ofusing, the new compounds to combat fungi, insects and acarids.

The present invention relates to and has for its objects 9 Claims theprovision of a process involving reacting the enol form of an amide oran imide of a carboxylic acid or carbonic acid, having at least onehydrogen atom on each of an oxygen and nitrogen or two nitrogen atomsvicinal to the amide carbon atom, with perfluoro-2,5-diazahexa-2,4-diene in the presence of a hydrogen fluoride acceptor at atemperature of about to 120 C., to form 4,5-bis-(trifluoromethylimino)-oxazoles or diazoles which are fungicidally,insecticidally and acaricidally active, with other and further objectsof the invention becoming apparent from a study of the withinspecification and companying examples. I

The present invention relates to the preparation of new4,S-bis-trifluoromethylimino derivatives 'of sulfur-free heterocyclicfive-membered rings with two ring hetero atoms of the general formula Ie d.1-Iene?2 1274 in which Z is oxygen, R--N= or X is oxygen or v v i!"and 1 R, -R',R" and R" are each hydrogen; alkyl, alkenyl or alkynyl withup to 8 .carbon atoms optionally substituted by I halogen, cyano,- loweralkoxyor alkylmercapto; optionally lower-alkyl substituted cycloalkyl;carbalkoxy; aralkyl with up, to 2 carbon atoms inthe alkyl moiety oraryl with up to 14 carbonatoms in the ring system, the aryl radicalsoptionally being substituted by halogen, cyano, nitro, lower alkyl,lower haloalkyl, lower. alkoxy or lower alkylmercapto; 5- to 7-memberedheterocyclic rings; or a radical which together with Z and X or theN-atom of the ring forms further 5- to 7-membered ring,"the heterocyclicrings optionally being substituted with halogen, cyano, nitro or loweralkyl, or being fused with a benzene ring which is optionally partiallyhydrogenated.

In preparing the novel compounds, the enol form of an amide or an imideof a carboxylic acid or carbonic acid having at least one hydrogen atomon each of an oxygen and nitrogen or two nitrogen atoms vicinal to theamide carbon atom is reacted with perfluoro-2,5- diazahexa-2,4-diene inthe presence of a hydrogen fluoride acceptor at a temperature of about-50 to 120 C. Specific'ally, a carbonic acid derivative or carboxylicacid derivative of the general formula N H v .v

in which X and Z have the meanings stated above, 7 i is reacted withperfluoro-2,5-diazahexa-2,4-diene' of i the formula F -C a I v in thepresence of a hydrogen fluoride acceptor at a temperature ofabout -50to120 C.

It is pointed out that the designation sulfur-free" has reference to theheterocyclic five-membered ring shown in Formula I'rather than to thesubstitutents which, as mentioned, may contain sulfur, e.g.alkylmercapto. v. It is very surprising that the above-mentionedcompounds of the Formula II can react with perfluoro-2,5'-'diazahexa-2,4-diene of the Formula III to give the hitherto unknownfive-membered ring systems of the Formula I smoothly and with goodyields. Furthermore it is surprising that the compounds according to theinvention possess diene are'used as starting materials, and sodiumfluoride is used as acid-binding agent, the reaction course can berepresented by the following formula scheme:

If 3-methyl-pyrazolone-(5), which reacts from its enol form, andperfluoro-Z,5-diazahexa-2,4-diene are used as starting materials, andsodium fluoride is used as acidbinding agent, the reaction course can berepresented by the following formula scheme:

The carbonic acid derivatives or carboxylic acid derivatives to be usedas starting materials are defined generally by the Formula II.

Preferably, R, R, R", R'" and R" are hydrogen; alkyl or alkenyl with upto 6 carbon atoms, optionally substituted by fluorine, chlorine, bromineand/or alkylmercapto; cyclopentyl or cyclohexyl; carbomethoxy or othercarbalkoxy groups containing from 2 to 5 carbon atoms in the alkoxygroup; benzyl, or aryl with up to carbon atoms in the ring system, thearomatic rings possibly being substituted by fluorine, chlorine,bromine, cyano, nitro, methyl, ethyl, isopropyl, chloromethyl,trifluoromethyl, methoxy and/or methylmercapto; 5- or 6-memberedheterocyclic rings or radicals which together with Z and X or the N-atomof the ring form a 5- or 6-membered ring, the heterocyclic ringsoptionally being fused with a benzene ring which may be partiallyhydrogenated. Most preferably, Z is oxygen and X is =NR', one R' beingmethyl and the other being phenyl or cyclohexyl optionally substitutedwith chloro or trifluoromethyl.

The carbonic acid derivatives and carboxylic acid derivatives of theGeneral Formula II to be used as starting materials are for the mostpart known and can be prepared in generally known manner; they areobtained for example when carbonic acid halides or carboxylic acidhalides are reacted with ammonia or amines; thus, many of the ureaderivatives of the General Formula II can be prepared in known mannerfrom primary amines and isocyanates; there are mentioned for example thefollowing isocyanates: p-trifluoromethylphenyl-isocyanate,p-nitrophenylisocyanate, methylisocyanate, isopropylisocyanate, tert.-butylisocyanate, cyclohexylisocyanate, allylisocyanate,fl-chloroethylisocyanate, phenylisocyanate, o-nitrophenylisocyanate,p-nitrophenyiisocyanate, m-nitrophenylisocyanate,o-chloro-phenylisocyanate, m-chloro-phenylisocyanate,3,4-dichloro-phenylisocyanate, p-chloro-phenylisocyanate,p-naphthylisocyanate, benzylisocyanate, stearylisocyanate,p-cyanoethylisocyanate, ethylisocyanate, n-propylisocyanate,n-butylisocyanate, isobutylisocyanate, Z-ethyI-hexylisocyanate,dodecylisocyanate, tetradecylisocyanate, hexadecylisocyanate, p methoxyphenylisocyanate, p-methylmercapto-phenylisocyanate; and the like.

As examples of primary amines, there are suitable, besides the amines onwhich the above isocyanates are based, the following amines for thepreparation of compounds of the Formula II:

Z-aminopyridine,

Z-amino-thiazole, Z-amino-benzthiazole,

Z-aminol-methyl-cyclohexane, hexahydro-benzyl-amine, Z-chloro-aniline,

3-nitroaniline, 2-chloro-4-nitro-aniline,

5 -chloro-2-amino-toluene, 4-chloro-3-amino-benzotrifluoride,1-amino-2-phenyl-ethane,

Z-amin 0-1 -isopropylb enzene, 5-amin0- 1 ,2,4-trimethylbenzene,5,6,7,8-tetrahydronaphthyl-amine-( 1 3 ,5 -dichlor oaniline,

2,4, S-trichloro aniline, 2,4-dichloroaniline,

2, 3-dichloroaniline, 2,5-dichloroaniline,

3-chloroaniline,

4-chloroaniline, 4-chloro-2-nitroaniline,

aniline,

2-nitro aniline,

4-nitroaniline,

5 -chloro-2-nitro-aniline, 4-chloro-3-nitroaniline,3-chloro-4-nitroaniline, 4,6-dichloro-2-nitroaniline,

2,5 -dichloro-4-nitroaniline, 2,6-dichloro-4-nitroaniline,Z-amino-toluene, 3-chloro-2-aminotoluene, 4-chloro-2-amino-toluene,

5-m'tro-4- amino- 1,3 -dimethy1-benzene, 6-nitro-4-amino-1,3-dimethyl-benzene, S-amino-1,3-dimethyl-benzene,S-amino-1,3-bis-trifiuoro-methyl-benzene, Z-amino-1,4-dimethyl-benzene,Z-aminol-methyl-3 -ethy1benzene, G-amino-1,2,4-trimethyl-benzene,2-amino-1,3 ,5 -trimethyl-benzene, 2-amino-1,3 -diethyl-benzene,4-amino- 1,3 -dimethyl-5-ethyl-benzene,4-amino-1-methyl-3,S-diethyl-benzene, 2-amino-1,3-diisopropylbenzene,5,6,7,S-tetrahydronaphthylamine- (2), fl-bromo-ethylamine,

l-cyano- 1 -phenyl-ethy1amine, 1-cyano-l-methyl-ethylamine,S-chIoro-Z-amino-benzo-trifluoride, 6-chloro-2-amino-toluene,

4, 5 -dichloro-2- amino-toluene, 3-nitro-2- amino-toluene,4-nitro-2-amino-toluene, 5-nitro-2-amino-toluene,6-nitr0-2-amin0-t0luene, 4-chloro-5-nitro-2-amino-toluene,

3 -amino-toluene, 4-chloro-3-amino-toluene, 6-chloro-3-amino-toluene,4,6-dichloro-3-amino-toluene, 4-amino-toluene, Z-chloro-4-amino-toluene,2-nitr0-4-amin0-tQ uene,

3-nitro-4-amino-toluene, 2-amino-1-ethylbenzene,l-amino-l-phenyl-ethane, 2,3-dimethyl-aniline, 2,6-dimethyl-aniline,3,4-dimethylaniline, 2,4-dimethylaniline, and the like.

The guanidines of the Formula II, such as 2-aminobenzimidazole, 2[aminocarbomethoxy) ]-benzimidazole, p-chlorophenylimido-N,N-diethylurea, are obtainable in manner known from the literature.

The perfluoro-2,5-diazahexa-2,4-diene of the Formula III to be used asstarting material is known (I. Am. Chem. Soc. 89, 5007 (1967)).

The reaction may be carried out in the presence of a diluent. Asdiluents, all inert organic solvents are suitable. Preferred solventsinclude hydrocarbons, such as benzine, benzene and toluene; nitriles,such as acetonitrile; and chlorinated hydrocarbons, such as methylenechloride, chloroform and chlorobenzene.

As acid-binders, all customary acid-binding agents can be used. Theremay be mentioned: alkali metal carbonates, alkali metal bicarbonates andtertiary amines, such as triethylamine, dimethylaniline, and the like.In particular the alkali metal fluorides, especially sodium fluoride,have proved to be hydrogen fluoride acceptors which are particularlyuseful in practice.

The reaction temperatures can be varied within a fairly wide range. Ingeneral, the reaction is carried out at about -50 to 120 0., preferablyabout 30 to 90 C.

In carrying out of the process according to the invention, for each moleof the compound of Formula II there is generally used 1 mole ofperfluoro-2,4-diazahexa- 2,4-diene of the Formula III; the alkali metalfluoride is desirably used in excess, e.g. about 3 to 4 moles, butamounts lesser or greater than the stated proportions by up to 20percent by weight can be used without substantial lowering of the yield.Expediently, the perfluoro-2,5 diazahexa-2,4-diene is added dropwise toa suspension comprising the compound of Formula II, organic solvent andhydrogen fluoride acceptor. Filtration from the fluoride is theneffected, followed by concentration and recrystallization. Anothermethod of working up consists in adding water to the reaction mixtureand, optionally, recrystallizing the residue obtained.

The active compounds of the invention exhibit a strong fungitoxicactivity. In the concentrations appropriate for the control of fungi,they generally do not damage cultivated plants and they have a lowtoxicity to warmblooded animals. For these reasons, they are suitablefor use as crop protection agents for the control of fungi. Fungitoxicagents in crop protection are used for the control of Archimycetes,Phycomycetes, Ascornycetes, Basidiomycetes and Fu ngi imperfecti.

The active compounds of the invention have a broad activity spectrum andcan be applied against parasitical fungi which infect above-the-groundparts of plants or attack the plants from the soil, as well as againstseed-borne pathogenic agents.

The compounds possess a good activity against F usicladium dendriticum,the causative organism of apple scab, against Phytophthora infestans,the causative organism of potato blight, and against Piricularia oryzae,the causative organism of rice blast.

The compounds according to the invention, however, also act againstother fungi which attack rice or other cultivated plants, such asMycosphaerella musicola, Verticillium alboatrum, Phialophora cinerescensand Fnsarium species.

The compounds according to the invention are distinguished by anextraordinarily high degree of activity and a very broad spectrumagainst phytopathogenic soil fungi and against seed-borne fungal plantdiseases. They can be used preferably as soil treatment agents and seeddressings and are superior in this respect to customary commercialpreparations. Surprisingly, the present active compounds show not only aprotective activity, but also a curvative and systemic efiect.

The compounds which can be prepared according. .to the process alsopossess an insecticidal and acaricidal elfectiveness. The products areused with success in crop protection for the control of noxious suckingand biting insects, Diptera and mites (Acarina), as Well as in theveterinary and hygiene field; further, in the protection of storedproducts against a multiplicity of animal pests such as endoparasitesand ectoparasites.

To the sucking insects contemplated herein there belong, in the main,aphids (Aphidae) such as the green peach aphid (Myzus persicae), thebean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi),the pea aphid (Macrosiphum pisi), and the potato aphid (Macrosiphumsolanifolii), the currant gall aphid (Cryptomyzus ko rschelti), the rosyapple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterus arundinis) and the cherry black-fly (Myzus cerasi); in addition, scales andmealybugs (Coccina), for example the cleander scale (Aspidiotus hederae)and the soft scale (Lecanium hesperidwm) as Well as the grape mealybug(Pseudococcus maritimus); thrips (Thysanoptera) such as Hercinothripsjemoralis, and bugs for example the beet bug (Piesma quadrata), the redcotton bug (Dysdercus intermedius) the bed bug (Climex lectularius), theassassin bug (Rhodnius prolixus) and Chagas bug (Triatoma infestans)and, further, cicadas, such as Euscelis bilobatus and Nephotettixbipunctatus; and the like.

In the case of the biting insects contemplated herein, above all thereshould he mentioned butterfly caterpillars (Lepidoptera) such as thediamond-back moth (Plutella maculipennis), the gypsy moth (Lymantriadispar), the browntail moth (Euproctis chrysorrhoea) and tentcaterpillar (Malacosoma neustria); further, the cabbage moth (Mamestmbrassicae) and the cutworm (Agrotis segetum), the large white butterfly(Pieris brassicae), the small winter moth (Cheimatobia brumata), thegreen oak tortrix moth (Tortrix viriddna), the fall armyworm (Laphygmafrugipera'a) and cotton Worm (Prodenia litura), the ermine moth(Hyponomeum padella), the Mediterranean flour moth (Ephestia kuh'niella)and greater wax moth (Galleria mellonella); and the like.

With the mites (Acari) there are classed, in particular, the spidermites (Tetrzmychidae) such as the two-spotted spider mite (Tetmnychustelarius-Tetranychus althaeae or Tetraanychus urticae) and the Europeanred mite (Paratetranychus pilosus-Panonychus ulmi), gall mites, forexample the black currant gall mite (Eriophyes ribis) and tarsonemids,for example the broad mite (Hemitarsonemus latus) and the cyclomen mite(Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick(Ornithodorus moubata); and the like.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e. plant compatible or herbicidally inert)pesticide diluents or extenders, i.e. diluents or extenders of the typeusable in conventional pesticide formulations or compositions, e.g.conventional pesticide dispersible carrier vehicles, such as solutions,emulsions, suspensions, emulsifiable concentrates, spray powders,pastes, soluble powders, dusting agents, granules, etc. These areprepared in known manner, for instance by extending the active compoundswith conventional pesticide dispersible liquid diluent carriers and/ordispersible solid carriers optionally with the use of carrier vehicleassistants, e.g. conventional pesticide surface-active agents, includingemulsifying agents and/ or dispersing agents, whereby, for example, inthe case where water is used as diluent, organic solvents may be addedas auxiliary solvents. The following may be chiefly considered for useas conventional carrier vehicles for this purpose: aerosol propellantswhich are gaseous at 7 normal temperatures and pressures, such as Freon;inert dispersible liquid diluent carriers including inert organicsolvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene,alkyi naphthalenes, etc.), halogenated, especially chlorinated, aromatichydrocarbons (e.g. chlorobenzenes), cycloalkanes {c.g. cyclohexane,etc), Paraffins (e.g. petroleum or mineral oil fractions), chlorinatedaliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g.methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethersand esters thereof (eg glycol monomethyl ether, etc.), amines (e.g.ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides(e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, methyl ethylketone, methyl isobutyl ketone, cyclohexanone, etc.) and/or water: aswell as inert dispersible finely divided solid carriers, such as groundnatural minerals (e.g. kaolins, alumina, silica, chalk), i.e., calciumcarbonate, talc, kieselguhr, etc.) and ground synthetic minerals (e.g.highly dispersed silicic acid, silicates, e.g.,

alkali silicates, etc.); whereas the following may be chiefly consideredfor use as conventional carrier vehicle assistants, e.g., surface-activeagents, for this purpose: emulsifying agents, such as non-ionic and/oranionic emulsifying agents (e.g. polyethylene oxide esters of fattyacids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates,alkyl sulfonates, aryl sulfonates, etc., and especially alkylaryl-polyglycol ethers, magnesium stearate, sodium oleate, etc.); and/ordispersing agents, such as lignin, sulfite waste liquors, methylcellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/ or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other fungicides oracaricides, insecticides, herbicides, bactericides, nematicides,fertilizers, growth regulating agents, etc., if desired, or in the formof particular dosage preparations for specific application madetherefrom, such as solutions, emulsions, suspensions, powders, pastes,and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about (Ll-95%, and preferably0.5- 90%, by weight of the mixture, whereas carrier composition mixturessuitable for direct application or field application generallycontemplate those in which the active compound is present in an amountsubstantially between about 0.000ll%, preferably at least 0.5% weight ofthe mixture. Thus, the present invention contemplates over-allcompositions which comprise mixtures of a conventional dispersiblecarrier vehicle such as (l) a dispersible inert finely divided carriersolid, and/or (2) a dispersible carrier liquid such as an inert organicsolvent and/or water preferably including a surface-active effectiveamount of a carrier vehicle assistant, e.g. a surfaceactive agent, suchas an emulsifying agent and/or a dispersing agent, and an amount of theactive compound which is effective for the purpose in question and whichis generally between about 01-95%, and preferably 0.5- 95 by weight ofthe mixture.

The active compounds can also be used in accordance with the well knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50- 100 microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/ hectare are needed,and often amounts only up to about 15 to 1000 g./hectare, preferably 40to 600 g./hectare, are suflicient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95% by weight of activecompound or even the 8. 100% active substance alone, e.g. about 20-100%by weight of the active compound.

In the case of seed treatment, in general amounts of active compound of0.01 to 50 g., preferably 0.01 to 5 g., per kilogram of seed are appliedas a seed dressing.

For soil treatment, in general amounts of active compound of 1 to 500g., preferably 10 to 200 g., are applied per cubic meter of soil. Theconcentrations of active compound in the ready-to-apply preparations mayvary very greatly. In general, they are from 0.0001 to Furthermore, thepresent invention contemplates methods of selectively killing, combatingor controlling pests, e.g. fungi, insects and acarids, which compriseapplying to at least one of correspondingly (a) such fungi, (b) suchinsects, to) such acarids and (d) the corresponding habitat thereof,i.e., the locus to be protected, a correspondingly combative or toxicamount, i.e. a fungicidally, insecticidally, or acaricidally effectiveamount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulationsor compositions are applied in the usual manner, for instance byspraying, atomizing, vaporizing, scattering, dusting, watering,sprinkling, pouring, via dressings, incrustations, and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases, it ispossible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding fungicidal and acaricidalactivity of such active compounds usable according to the presentinvention is illustrated, without limitation, by the following examples.

EXAMPLE 1 Mycelium growth test 20 parts by weight agar-agar 200 parts byweight potato decoction 5 parts by weight malt 15 parts by Weightdextrose 5 parts by weight acetone 2 parts by weight Na HPO 0.3 part byweight Ca(NO Proportion of solvent to nutrient medium:

2 parts by Weight acetone parts by weight agar nutrient medium Theamount of active compound required for the desired concentration ofactive compound in the nutrient medium is mixed with the stated amountof solvent. The concentrate is thoroughly mixed in the stated proportionwith the liquid nutrient medium which has been cooled to 42 C. and isthen poured into Petri dishes of 9 cm. diameter. Control dishes to whichthe preparation has not been added are also set up.

When the nutrient medium has cooled and solidified, the dishes areinoculated with the species of fungi stated in the table and incubatedat about 21 C.

Evaluation is carried out after 4-10 days, dependent upon the speed ofgrowth of the fungi. When evaluation is carried out theradial growth ofthe mycelium on the treated nutrient media is compared with the growthon the control nutrient media. In the evaluation of the fungus growth,the following characteristic values are used:

0=no fungus growth 1=very strong inhibition of growth 2=mediuminhibition of growth 3=slight inhibition of growth 4=growth equal tothat of untreated control.

The active compounds, their concentrations and the results obtained canbe seen from Table 1.

TABLE r; Myoelium growth test v Couceutrav Mucotion of C'ochliov 1Vcrtl- Couch Phiahu, Cacosphae- PM- active bolus Fusarium -FuauriumPelliclllium trlchum phom apora rella culo compound, Botrutls miua-02:11.21). 2. ozyspJ. culurlo. albocoflecinerpersomusiria Activecompounds p.p.m. cinerea beanus cubeme .dianthl aasakii 02mm anum mmnato cola oryzae 311; 10 o o .0 o

=NCF| 0: (4)

|-=NCF:

G1 I ([JH; 10 o o N-=NCF| 0= (5) III-=NOF| EXAMPLE 2 TABLE 2-- ContinuedFusicladmm test (apple scab) (protective) I t g fgl ti percentage ofSolvent: 4.7 parts by weight acetone fig 2 1 Emulslfier: 0.3 part byweight alkylaryl polyglycol ether concentration of active Water: 95parts by weight g ff (in permit) 'The amount of active compound requiredfor the de- Active compound 0,0 62 1 6 sired concentration of the activecompound in thef spray liquid is mixed with the stated amountof solvent,and CH: 0 5 the concentrate is diluted with the stated amount ofwater--=N-CF| which contains the stated additions.

Young apple seedlings in the 4-6 leaf stage are sprayed 40 with thespray liquid until dripping wet. The plants re- (4) main in a greenhousefor 24 hours at 20 C. and at a relative atmospheric humidity of 70%.They are then inoculated with an aqueous conidium suspension ,of theapple scab causative organism (Fusz'cladium dendriticum 5 el) andincubated for 18 hours in a humidity cham- (31 her at 18-20 C. and at arelative atmospheric humidity CH a o a of 100%. I

The plants are then again placed in a greenhouse for 0 14days., Y 15days after inoculation, the infection of the seedlings N is determinedas a percentage of the untreated but also (5) inoculated control plants.

0% means no infection; 100% means that the infection is exactly as greatas in the case of the control plants. 5

The active compounds, the concentrations of the active Y I compounds andthe results can be seen from Table 2: 0 0

TABLE2 Fusicladium test (protective) h 7 iv I Infection asapercentage o!-C C l :he tinflection; 01f thiefllmv e cfuae ntrg tgrfoiwactiv 59 N Ccgmpound (in percent) v. Activeeompound 10.0062 0.00156 EXAMPLE 3 O 26 g2 Fusicladium test (apple scab) (curative) J5 Solvent: 4.7parts byweight acetone Emulsifier: 0.3 part by weight alkylaryl polyglycol etherN-S-C on (A) 76 Water: parts by weight. 0 i The amount of activecompound required for the dea sired; concentration of the activecompound in the spray liquidis mixed with the stated amount of solvent,and (known) the concentrate is diluted with the stated amountof waterwhich contains the stated additions.

Young apple seedlings in the 4-6 leaf stage are inoculated with anaqueous conidium suspension of the apple scab causative organismFusiclad'ium dendriticum el and incubated for 18 hours in a humiditychamber at 18-20 C. and at an atmospheric humidity of 100%. The plantsare then placed in a greenhouse where they dry.

After standing for a suitable period of time, the plants are sprayeddripping wet with the spray liquid prepared in the manner describedabove. The plants are then returned to a greenhouse.

15 days after inoculation, the infestation of the apple seedlings isdetermined as a percentage of the untreated but also inoculated controlplate.

means no infestation; 100% means that the infestation is exactly asgreat as in the case of the control plants.

The active compounds, the concentrations of the active compounds, theperiod of time between inoculation and spraying and the results obtainedcan be seen from Table 3.

TABLE 3 Fusicladium test (curative) Infestation as e percentage of theinfection of the untreated control with a concentration of activecompound (in percent) of Resideuce period in hours Active compound NHCuHzsNH-C -CH;COOH

(known) EXAMPLE 4 Fusicladium test (systemic) The amount of activecompound required for the desired concentration of the active compoundin the liquid to be used for watering is mixed with the stated amount ofsolvent, and the concentrate is diluted with the stated amount of waterwhich contains the stated additions.

Apple seedlings grown in standard soil are, in the 3-4 leaf stage,watered once in one week with 20 cc. of the liquid to be used forwatering, in the stated concentration of active compound, with referenceto 100 cc. of soil. The plants so treated are, after the treatment,inoculated with an aqueous conidium suspension of Fusicladiumdendriticum el and incubated for 18 hours in a humidity chamber at l820C. and at a relative atmospheric humidity of 100%. The plants are thenreturned to a greenhouse for 14 days.

15 days after inoculation, the infection of the seedlings is determinedas a percentage of the untreated but also inoculated control plants. 0%means no infection; 100% means that the infection is exactly as great asin the case of the control plants.

The active compounds, the concentrations of the active compounds and theresults Obtained can be seen from Table 4.

TABLE 4 Fusicladium test (systemic) Active compound Iniestation 1 As apercentage of the infection of the untreated control with aconcentration of active compound of 15 p.p.m.

EXAMPLE 5 Phytophthora test Solvent: 4.7 parts by weight of acetoneDispersing agent: 0.3 part by weight of alkylarylpolyglycol ether Water:parts by weight The amount of the active compound required for thedesired concentration of the acive compound in the spray liquid is mixedwith the stated amount of solvent and the concentrate is diluted withthe stated amount of water which contains the stated additions.

Young tomato plants (Bonny best) with 2-6 foliage leaves are sprayedwith the spray liquid until dripping wet. The plants remain in agreenhouse for 24 hours at 20 C. and at a relative atmospheric humidityof 70%. The tomato plants are then inoculated with an aqueous sporesuspension of Phytophthora infestans. The plants are brought into amoist chamber with an atmospheric humidity of and a temperature of l8-20C.

After days the infestation of the tomato plants is determined as apercentage of the untreated but likewise inoculated control plants: 0%means no infestation; 100% means that the infestation is exactly asgreat as in the case of the control plants.

The active compounds, the concentrations of the active compounds and theresults can be seen from the following table:

to be used for watering is mixed with the stated amount of solvent, andthe concentrate is diluted with the stated amount of water whichcontains the stated additions.

EXAMPLE 6 Podosphaera test (powdery mildew of apples) (protective)Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 .part by. weightalkylaryl poly'glycol ether Water: 95parts by weight The amount ofactive compound required for the desired concentration of the activecompound in the spray liquid is mixed with the stated amount of solvent,and the concentrate is diluted with the stated amount of water whichcontains the stated additions.

Young apple seedlings in the 4-6 leaf stage are sprayed with the sprayliquid until dripping wet. The plants remain in a greenhouse for 24hours at 20 C. and at a relative atmospheric humidity of 70%. They arethen inoculated by dusting with conidia of the apple powdery mildewcausative organism (Podosphaera leucotricha Salm.) and placed in agreenhouse at a temperature of 21- 23 C. and at a relative atmospherichumidity of about 70%.

Ten days after the inoculation, the infestation of the seedlings isdetermined as a percentage of the untreated but also inoculated controlplants.

means no infestation; 100% means that the infestation is exactly asgreat as in the case of the control plants.

The active compounds, the concentrations of the active compounds and theresults obtained can be seen from the following Table 6:

TABLE 6 Podosphaera test (Protective) Infection as a percentage of theinfection of the untreated control with a concentration of active c fmpound (in percent) 0 Active compound 0. 0062 0. 00156 --N=CF, o=-[=NCF| N=C-S 5 45 71 t v co N=os ,(Oxythioqninox) (known) v (1d.N-ooo-om F CN= N-CFi' EXAMPLE 7 Pd s le t y t mi Solvent: 4.7 parts byweight acetone Dispersing agent: 0.3 part by weight alkylaryl polyglycolether Water: 95 parts by weight The amount of active compound requiredfor the desired concentrationuofrthe,v activencompoundin the. liquidApple seedlings grown in standard soil are, in the 3-4 leaf stage,watered in one week with 20 cc. of the liquid plants so treated are,after the treatment, inoculated with conidia of Podosphaera leucotrichaSalm. and placed in a greenhouse at a temperature of 21-23 C. and at arelative atmospheric humidity of about 70%. 10 days after theinoculation, the infection of the seedlings is determined as apercentage of the untreated but also inoculated control plants. Y

0% means no infection; 100% means that the infection is exactly as greatas in the case of the control plants.

The active compounds, the concentrations of the active compounds and theresults obtained can be seen from the following Table 7:

TABLE 7 Podosphaera test (systemic) Infection as a percentage of theinfection of the untreated control with a concentration of activecompound of- Active compound 30 p.p.m.

EXAMPLE 8 Agar plate test Test for fungitoxic effectiveness and breadthof the activity spectrum.

Solvent: Actone Parts by weight: (a) 1000; (b) 100 To produce a suitablepreparation of the active compound, 1 part by weight of the activecompound is taken 15 p.p.m.

up in the stated amount of solvent.

To potato dextrose agar which has been liquefied by heating there isadded the preparation of the active compound in such an amount that thedesired concentration of active compound is set up therein. Afterthorough shaking to achieve a uniform dispersion of the active compound,the agar is poured into Petri dishes under sterile conditions-When themixture of substrate and active compound has solidified, test fungi frompure cultures are inoculated onto it in small discs of 5 mm. diameter.The Pet'ri dishes remain at 20 C. for 3 days for incubation.

I After this time, the inhibiting action of the active compound on themycelium growth is determined in categories, taking into account theuntreated control. 0 means no mycelium growth, either on the treatedsubstrate or on the inoculum; the symbol means mycelium growth on theinoculum only but no spread to the treated sub strate; and the symbolmeans mycelium growth from the inoculum onto the treated substrate,similar to the spread to. the untreated substrate of the control.

The active compounds, the concentration of the active compounds, thetest fungi and the inhibition eifects achieved'can be seen from thefollowing Table 8.

' TABLE 8 Agar plate test Concentration of active compound in the Corti-Sclerotinia Verti- Thiela- Phyio- Fusariu-m substrate cium sclemcilliumuiopsis phthora Fusarium Fusarium solo Active compound in ppm. mlfsiitiomm clboatrum basicola caclomm culmomm ozyspmm 12551 U t u (@158 i i i*5 i i i i CH:NHC S Zn (B) CH:NH[CI S (known) CH; (2) 10 0 0 0 0 0 0 0 I(b) 100 0 0 0 0 0 0 0 0 N=NC Fl 0= (1) I'\T""NC F; CH;

CH; (a) 10 0 0 0 0 0 l (b) 100 0 o o 0 0 0 -JC F 0= (4) N-=N-C F;

CH; (a) 10 0 0 0 0 0 0 0 0 I (b) 100 0 0 0 O 0 0 0 0 N--=NC F; (5) N=N-C F;

CH (a) 0 0 0 0 l (b) 100 0 o o 0 o N-=NCF; 1) N =NC F:

EmMPLE 9 After 12 days, the infection of the cucumber plants isdetermined as a ercentage of the untreated but also P Erysiphe test(systemic) Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 part byweight alkylaryl polyglycol ether Water: 95 parts by weight The amountof the active compound required for the desired concentration in theliquid to be used for watering is mixed with the stated amount of thesolvent, and the concentrate is diluted with the stated amount of watercontaining the stated additions.

Cucumber plants grown in standard soil are, in the oneto two-leaf stage,watered three times in one week with 20 cc. of the liquid to be used forwatering, in the stated concentration of active compound with referenceto 100 cc. of soil.

The plants so treated are, after the treatment, inoculated with conidiaof the fungus Erysiphe cichoracearum. The plants are subsequently placedin a greenhouse at 2 a d at a r lative atmospheric humidity of 70%,

inoculated control plants. 0% means no infection; means that theinfection is exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and theresults obtained can be seen 17 EXAMPLE 10 Seed dressing test/ bunt ofwheat (seed-borne mycosis) To produce a suitable dry dressing the activecompound is extended with a mixture of equal parts by weight of talc andkieselguhr to give a finely powdered mixture with the desiredconcentration of the active compound.

Wheat seed is contaminated with 5 g. of the chlamydo spores of Tilletiacaries per kg. of seed. To apply the dressing, the seed is shaken withthe dressing in a closed glass flask. The seed, on moist loam under acover of a layer of muslin and 2 cm. of moderately moist compost soil,is exposed to optimum germination conditions for the spores for 10 daysat 10 C. in a refrigerator.

The germination of the spores on the wheat grains, each of which iscontaminated with about 100,000 spores, is subsequently determinedmicroscopically. The smaller the number of spores which have germinated,the more effective is the active compound.

The active compounds, the concentrations of the ac tive compounds in thedressing, the amounts of dressing used and the percentage sporegermination can be seen from the following Table 10.

TABLE 10 Seed dressing test (bunt of wheat) Concentraon ectivg A u d 8corn oun pp a P inthe amount of germidressingin dressing nation percentby lug/kg. in Active compounds weight seed percent Nonqimasnrl 16 10 1 5II 30 1 0.05 CHr-NHCS n CHr-N'HfiS (known) WCH: 30 1 0.05 AN (3) CFg-Np-=N-C F;

F 10 1 0.000 C a0 1 0.000 L I? N-CF:

|NJCF; 0=

N- =NCF:

EXAMPLE 11 Seed dressing test/stripe disease of barley (seed-bornemycosis) To produce a suitable dry dressing, the active compound isextended with a mixture of equal parts by weight of talc and kieselguhrto give a finely powdered mixture with the desired concentration ofactive compound.

To apply the dressing, barley seed, which is naturally infested byHelminthosporium gramineum, is shaken with the dressing in a closedglass flask. The seed, on moist filter paper discs in closed Petridishes, is exposed to a temperature of 4 C. for 10 days in arefrigerator. The germination of the barley, and possibly also of thefungus spores, is thereby initiated. Two batches of 50 grains of thepregerminated barley are subsequently sown 2 cm. deep in Fr-uhstorferstandard soil and cultivated in a greenhouse at temperatures of about 18C. in seed boxes which are exposed to light for 16 hours daily. Thetypical symptoms of the stripe disease develop within 3 to 4 weeks.

After this time, the number of diseased plants is determined as apercentage of the total number of emerged plants. The fewer plants arediseased, the more effective is the active compound.

The active compounds, the concentration of the active compounds in thedressing, the amounts of dressing used and the number of diseased plantscan be seen from Table 11.

1 As a percentage of the total number of emerged plants.

EXAMPLE 12 Soil treating agent test/soil-borne mycoses To produce asuitable preparation of the active compound, the active compound isextended with talc to a content of 5% and subsequently with quartz sandto a content of 0.5% of active compound.

The preparation of the active compound is uniformly mixed withFruhstorfer standard soil, which has first been sterilized and theninoculated with pure cultures of the test fungi.

The soil is filled into 5 pots, each of which is sown with 10 seeds ofthe host plants. The pots are placed in a greenhouse at the statedtemperatures and kept normally moist.

3 weeks after sowing, the number of healthy plants is determined as apercentage of the number of seeds sown. 0% means that no healthy plantshave grown; means that healthy plants have resulted from all the seeds.

The active compounds, the concentrations of the active compounds in thesoil, the test fungi, host plants, greenhouse temperatures and theresults obtained can be seen from Table 12.

TABLE 12 Soil treating agent test (soil-borne mycosis) Test fungi RhizoFusarium aolani cul'mormn Concentra- Host plant Pea tion of Pee Peeactive compound Temperature range 11 mg. Active compounds liter soil18-22 22-25 Fruhstorfer standard soil sterilized untreated 95 90Frnhstorter standard soil sterilized and inoeifleteduntIBtltBd.------..-----..---------.---.-;.-..--; 20

S- 100 2 2 Ulla-NR3 8 Zn (B) H NHE S (known) CH: 100 I so =N-CF: 25 1) NN-CFI in.

=NC Fl 0= (o N-C Fl EXAMPLE 13 Phaedon larvae test Solvent: 3 parts byweight dimethyl formamide Emulsifier: 1 part by weight alkylarylpolyglycol ether To produce a suitable preparation of active compound, 1part by weight of the active compound is mixed with the stated amount ofsolvent containing the stated amount of emulsifier, and the concentrateis diluted with water to the desired concentration.

Cabbage leaves (Brassz'ca oleracea) are sprayed with the preparation ofthe active compound until dripping wet and then infested with mustardbeetle larve (Phaedon cochleariae).

After the specified periods of time, the degree of destruction isdetermined as a percentage: 100% means that all the bettle larvae arekilled. 0% means that none of the beetle larvae are killed.

The active compounds, the concentration of the active compound, thetimes of evaluation and the results can be seen from the following Table13.

TABLE 13 (Plant-damaging insects) Phaedon larvae test Concentration ofDegree 0! active destruction compound in percent Active compounds inpercent after 3 days CH: 0. 2 0.02 o

N-C H=N G1 (known) FaC-N- -NCH; 0. 2 (5) 0.02 70 F|CN= N 0 INC-N N-CH:0.2 100 0. 02 30 FaC-N -0 1 ;C-N= -'NC H: 0. 2 100 (12) 0.02 30 FQCN=\NO F:CN=N-CH 0.2 100 (7) 0. 02 70 F;C-N= N 0 EXAMPLE 14 Tetranychus test(resistant) Solvent: 3 parts by weight acetone Emulsifier: 1 part byweight alkylaryl polyglycol ether To produce a suitable preparation ofactive compound, 1 part by weight of the active compound is mixed withthe stated amount of solvent containing the stated amount of emulsifierand the concentrate so obtained is diluted with water to the desiredconcentration.

Bean plants (Phaseolus vulgaris), which have a height of approximately10-30 cm., are sprayed with the preparation of the active compound untildripping wet. These beans plants are heavily infested with spider mites(Tetranychus urticae) in all stages of development.

After the specified periods of time, the effectiveness of thepreparation of active compound is determined by counting the dead mites.The degree of destruction thus obtained is expressed as a percentage:100% means that all the spider mites are killed whereas 0% means thatnone of the spider mites are killed.

The active compounds, the concentrations of the ac- TABLE 14(Plant-damaging insects) Tetranychus test (resistant) Concentration ofDegree of active destruction compound in percent Active compounds inpercent after 8 days CH; 0. 2 100 NC H=N 0-0 0-NH-CH; 0. 02 0 (known) F=-NC 0. 2 100 N 0. 02 90 5 FICN=\N O ='NCH 0. 2 100 m0 N 0.02 90 FrCH=-O EXAMPLE 15 Plutella test Solvent: 3 parts by weight dimethylformamide Emulsifier: 1 part by weight alkylaryl polyglycol ether Toproduce a suitable preparation of active compound,

1 part by weight of the active compound is mixed with the stated amountof solvent containing the stated amount of emulsifier and theconcentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation ofthe active compound until dew moist and are then infested withcaterpillars of the diamondback moth (Plutella maculipennis).

After the specified periods of time, the degree of destruc tion isdetermined as a percentage: 100% means that all the caterpillars arekilled whereas 0% means that none of TABLE 15Continued Concentration ofDegree of active destruction compound in percent Active compounds inpercent after 3 days FzC-N=-NCH: 0. 2 100 0. 02 100 0.002 50 FaC-N= 0F:CN= 'NC H: 0. 2 100 0. 02 C 0 (12) F: ---N-- N F|CN= NC HI 0. 2 0. 02100 F C N O (7) The following further examples are set forth toillustrate, without limitation, the process for producing the activecompounds according to the present invention.

EXAMPLE 17 N-q -NCF;

Analogously with Example 16, with acetamide instead of N,N'-dimethylurea there is obtained the above compound. The melting point (fromether/pentane) is 90- 92 C. (with decomp.) Mass spectrum: 247 m/e.

EXAMPLE 18 H O=NO Fr (3) To 10 g. (0.1 mole) of 3-methyl-pyrazolone-(5)and 15 g. of sodium fluoride in 100 ml. of acetonitrile there are addeddropwise, at a temperature of -30 C., 23 g.

r 3 (0.1 mole) of perfluoro-2,5-diazahexa-2,4-diene. Stirring isafterwards effected for 2 hours at C., followed by filtration fromsodium hydrogen fluoride and sodium fluoride and concentration of thefiltrate in a vacuum. After recrystallization from ether/hexane there isobtained the compound of the above formula of the M.P. 95-96" C.

EXAMPLE 19 Analogously with Example 16, with N-p-chlorophenyl- -methy1urea instead of N,N'-dimethyl urea there is obtained the compound of theabove formula of the M.P. 172-173 C. Yield: 92% of theory.

EXAMPLE 20 Analogously with Example 16, with N-phenyl-N'- methyl ureainstead of N,N'-dimethyl urea there is obtained the compound of theabove formula of the M.P. 159-160" C. Yield: 89% of theory.

Analogously with Example 18, with N-phenyl urea instead of3-methyl-pyrazo1one-(5) there is obtained the compound of the aboveformula of the M.P. 162-163" C.

EXAMPLE 22 Analogously with Example 16, with N-cyclohexy 1-N'-methyl-urea there is obtained the compound of the above formula of M.P.135-136" C. Yield: 70% of theory.

24 EXAMPLE 23 Analogously with Example 16, withN-3,4-dichlorophenyI-N'-methyl urea there is obtained the above compoundof the M.P. 149-150 C. Yield: 84% of theory.

EXAMPLE 24 Analogously with Example 18, withp-chlorophenylimido-N,N'-diethyl urea there is obtained the abovecompound of the M.P. -96" C. Yield: 69% of theory.

EXAMPLE 25 compound of the M.P. 152-153" C. (decomp.) (from acetone).Yield: 74% of theory.

EXAMPLE 26 I NH F30 F 3 (11) Analogously with Example 18, withZ-amino-benzimidazole there is obtained the above compound of the M.P.C. (with decomposition). Yield: 70% of theory.

EXAMPLE 27 Analogously with Example 12, withN-(3-chloro-4-trifluoromethyl)-phenyl-N'-methyl urea there is obtainedthe above compound of the M.P. 95-96 C. Yield: 75% of theory.

2 EXAMPLE 28 3. The compound according to claim 1 of the formula N-=NCF; o=o $3 5 1;z-=Nc F, N-=N-CFa CH: 0:0

\ 4. The compound according to claim 1 of the formula =NCF; 0=C/ (1a)N=NCF| Analogously with Example 12, with N,N'-diphenyl urea there isobtained the compound of the above formula of M.P. 197 to 198 C. Yield:70% of theory.

EXAMPLE 29 1 02H 5. The compound according to claim 1 of the formulaN==NC F] GE 1% N--=NCF; =N-C PI N-=NOF| (5) Analogously with Example 14,with Z- erimidinecarbamic acid ethyl ester there is obtained thecompound of 6. The compound according to claim 1 of the formula theabove formula of M.P. 150 C. (decomp.). Yield: 73% of theory.

EXAMPLE 30 cm I N--=NGF| O==C/ N-=Ncm l N 0C2H F;CN --CF; (15) (7) 7.The com ound accordin to l 1 f th f l Analogously with Example 18, withZ-amino-(carbo- P l g c m o e ormua ethoxy)-benzimidazole there isobtained the above compound of M.P. 108 C. (decomp.). Yield: 76% oftheory.

It will be appreciated that the instant specification and i examples areset forth by way of illustration and not N-=N |F limitation, and thatvarious modifications and changes may be made without departing from thespirit and scope N=N F:

of the present invention.

What is claimed is: 1. A 4,5-bis trifluoromethyl imino-diazole of theformula 1 F; 12 i N-=NCI*a o=c 8. A 4,S-brs-tnfluoromethyl-imino-diazoleof the for- N. =N-or, mula --N in which each R independently is alkyl ofup to 8 carbon I atoms, cyclopentyl, cyclohexyl, phenyl, or phenylmonoor di-substituted with halo, nitro, CF lower alkyl, lower \N M70001"alkoxy or lower alkylthio.

2. A compound according to claim 1, in which one R F'G N N43! is methyl.in which R is lower alkoxy.

. 27 28 9. The compound according to claim 8 of the .formula Lozinskiiet. aL: Chem. Abst., v01. 73, No. 14767z (197D). Parker: Chem. Abst.,vol. 70, No. 4112f (1969).

' I Todd et aL: Chem. Abst., vol. 40, columns 6467-9 \N (1946).

Walter: Chem. Abst., vol. 44, columns 10374 (1950).

F;CN= N-GF: (10) NATALIE TROUSOF, Primary Examiner References Cited 10Us. 01. X.R.

Dinwoodie et aL: Chem. AbsL, vol. 70, NO. 68367:! 260260307 R, 307 C,307 F, 309.6, 309.7, 518 R, 534 (1969). R, 553 R, 553 A, 564 A, 564 E,565; 424272, 273

Lozinskii et aL: Chem. Abst., vol. 73, No. 148481) (1970).

Patent No. 3,787,435

UNITED STA'IES PATENT OFFICE 1 CERTIFICATE OF CORRECTION Inventor(s) andthat said Letters Patent are hereby corrected as Col.

Col.

Col.

Col.

Hans-Joachim Scholl et a1 It is certified that error appears in theaboyc-ident'ified patent 3, line 12, 6, line 54,

9, line. 66,

12, line 37, change "After days" 19, Table 12 20, Table 13, Compound.(5) 22, line .46,

shown below:

Compound -(l) change "+2NaHF" to ZNaHF I correct spelling of 'cyclamen".

Table 2 last column, under heading'-'O. O0l56" cancel"0" at end of solidline, '15" to 50 l and change to After daysv in heading of secondcolumn, delete "Pea".

Under heading Test Fungi", change "Rhizo" to -Rhizoct.-

change "F C-N to F C-'N= correct spelling of "benzene".

, insert after line 6 Mass Spectrum: [286- m/e 23, Example 20, Compound(5) correct to read as follows .Patent No.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3,787,435 DatedJanuar 22, 1974 Hans-Joachim Scholl et al. Page 2 Inventor(s) It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Col. 24, line 72, change "12" to 16 C01. 25, line 16, change "12" to l6Col. 25, 'line 33, change "14" to 18 Signed and sealed this 22nd day ofOctober 1974.

(SEAL) Attest:

MCCOY M. GIBSON JR. 0. MARSHALL DANN Commissioner of Patents AttestingOfficer fuscomm-oc suave-ps9 U.S GOVERNMENT PRINTING OFFICE: 9

)RM PO-IOSO (10-69]

4.5-BIS-(TRIFLUOROMETHYLIMINO)OXAZOLES OR DIAZOLES ARE PREPARED BYREACTING THE ENOL FORM OF AN AMIDE OR AN IMIDE OF A CARBOXYLIC ACID ORCARBONIC ACID, HAVING AT LEAST ONE HYDROGEN ATOM ON EACH OF AN OXYGENAND NITROGEN OR TWO NITROGEN ATOMS VICINAL TO THE AMIDE CARBON ATOM,WITH PERFLUORO-2,4-DIAZAHEXA-2,4-DIENE IN THE PRESENCE OF A HYDROGENFLUORIDE ACCEPTOR AT A TEMPERATURE OF ABOUT -50 TO 120*C., IN ACCORDANCEWITH THE FOLLOWING FORMULA